REACTIONS OF ALCOHOL

OXIDATION REDUCTION

RXNS
OF
ALCOHOL

CARBON – OH BOND ALCOHOL TO ALKYL

BREAKING HALIDE CONVERSION
REACTIONS OF ALCOHOL
Summary

A. Oxidation

-In organic chemistry, increasing the number of bonds to

oxygen is considered an oxidation.
-Alkanes can be oxidized to alcohols (1 bond to oxygen,
which in turn can be oxidized to aldehydes or ketones (2
bonds to oxygen).
-Aldehydes can be further oxidized to the carboxylic acid
(3 bonds to oxygen).
-Tertiary alcohols cannot be oxidized!!
- ROH is main source for obtaining C=O.
NOTE:
Oxidation of 1o & 2o alcohol will give aldehyde and ketone
respectively.
1o alcohol (Hot Cu or Collins reagent (CrO3, pyridine or
pyridinium chlochromate. )
For the 2o alcohol, (chromic acid, H2CrO4 or chromium
trioxide (CrO3) (a powerful oxidizing agent)
-General Eqn & Example:

green

Cr 3+

-if H2CrO4 is used on 1o alcohol, the product of rxn will be

carboxylic acid.
Note: H2CrO4 reagent is used as a visual test to
differentiate classes of alcohols.

i. Primary alcohol
H2CrO4
CH3CH2CH2OH CH3CH2COOH Cr 3+
green
1-propanol (1o) propanoic acid green

ii. Secondary alcohol

OH O

H2CrO4 Cr 3+

green
Cyclohexanol cyclohexanone
iii. Tertiary alcohol
CH3
H2CrO4
H3C C CH3 NO REACTION
OH
2-methyl-2-propanol

B. Reduction by TsCl
-product of rxn is alkane.
-reagents used are either para-toluenesulfonic chloride or
tosyl chloride (TsCl) in pyridine to give tosylate ester.
-Reduction of ester tosylate by LiAlH4 is alkane.
General Eqn:

Example:

OH OTs

TsCl LiAlH4
pyridine
Cyclohexanol tosylate ester cyclohexane

What about the mechanism?

Summary of Reaction of Tosylate Esters

C. Breaking of Carbon-Hydroxyl Bond

-this rxn is used to convert alcohol to another functional
grps.

Examples:
a. Alcohol to Alkyl Halide Conversion
-rxn of substitution of OH with halide ion by using
halogenation reagent to form alkyl halide
-There are 3 ways to do so.
i. Rxn with HCl (Lucas Test)
General eqn:
ZnCl2 , H2O
R-OH + HCl R-Cl

-the mixture of HCl and ZnCl2 is called Lucas reagent.

- a cloudy mixture indicate presence formation of alkyl
halide.
-Alcohol reactivity towards Lucas reagent is as below:
3o ROH > 2o ROH > 1o ROH
(instantaneous) (after 5 mins) (no rxn)

Note: LUCAS REAGENT is used as VISUAL TEST for

different of alcohol. Examples:

a. 3o ROH
ZnCl2 , H2O
(CH3)3COH + HCl (CH3)3CCl + H2O
(Cloudy instantaneous)

b. 2o ROH
(CH3)2CHOH + HCl ZnCl2 , H2O (CH3)2CHCl + H2O
(Cloudy after 5 mins)

c. 1o ROH ZnCl2 , H2O

CH3CH2CH2OH + HCl No Rxn

ii. Rxn with thionyl chloride, SOCl2

General eqn:

- SO2 is the best halogenation reagent to convert alcohol

to alkyl halide
Examples:

CH3(CH2)5CH2OH + SOCl2 CH3(CH2)5CH2Cl

1-heptanol 1-chloroheptane

+ SO2 + HCl
iii. Rxn with phosphorus trihalide, PX3
General eqn:

3ROH + PX3 3RX + H3PO3

(PX3:PCl3, PBr3 or PI3)

-involves substitution of nucleophile.

-rxn of 3o ROH with PX3 is quite difficult but progress
easily for 1o & 2o ROH with high yield.
Examples:

CH3OH PBr3 CH3Br

CH3(CH2)14CH2OH + PI3 CH3(CH2)14CH2I

CH3CHCH3 + PBr3 CH3CHCH3

OH

b. Dehydration of alcohol to form alkene

-product of rxn follows Saytzeff rule.
- This is a reversible rxn.
-Dehydrating reagents are concn. H2SO4 or concn H3PO4
heated to 100-200oC.
-Reactivity of dehydration of alcohols are as below:
Tertiary > secondary > primary

Example:
i.
OH
CH3
H2SO4

major minor
ii.
OH
H2SO4

cyclohexanol cyclohexene

Mechanism of dehydration
The dehydration of cyclohexanol with H2SO4 has 3 steps;
1. Protonation of the hydroxide
2. Loss of water
3. Deprotonation.

-Dehydration of ROH is a reversible rxn and products are

separated by fractionation.
-The alkene formed is usually a result from formation of
the most stable carbocation.
- Hydride shift is often occur to achieve the most stable
carbocation to give stable alkene. (sometimes vice versa)

Example:
Show by using rxn mechanism of dehydration of 2-
methyl-2-butanol and show which is the major and minor
product.
Answer:
CH3 CH3 H CH3
CH3CH2CCH3 H2SO4 CH3CH2CCH3 CH3CHCCH3
3ocarbocation
OH OH2

H CH3 H CH3
CH3CHCCH3 CH3CH CCH3

2ocarbocation 3ocarbocation

hydride -H+
shift

CH3 CH3
H2C CHCHCH3 CH3CH=CHCH3
minor major

c. Dehydration of Alcohol to form Ether

-rxn is catalyzed by an excess of strong acid at 140oc to
yield symmetrical ether.
-Caution:
Temp > 140oC does not give ether but alkene!
Examples:
H2SO4, 140oC
2CH3CH2OH CH3CH2OCH 2CH3 H2O
Ethanol diethyl ether

H 2SO4, 140oC
2CH3OH CH 3OCH3 H2O
Methanol dimethyl ether
d. Cleavage of Oxygen-Hydrogen Bond
The above bonds on alcohols can be broken by these
rxns:
i. Formation of Salts
ii. Formation of Organic Ester
iii. Formation of Inorganic Ester

i. Formation of Salts
-The H on the OH group is acidic and can be removed
from alcohol by using metal i.e Na/K, and the product is
an alkoxide salt.
Examples:
2ROH 2Na 2RO-Na+ H2

2ROH 2K 2RO-K+ H2

Reactivity of rxn is CH3 > 1o > 2o > 3o. For rxn of 3o or 2o

ROH, the more reactive K is used.
ROH NaOH No reaction

ii. Formation of Organic Ester (Fischer

Esterification)

-Involves reaction of alcohol with carboxylic acid in

presence of an acid catalyst.
-A reversible rxn & difficulty to obtain high yield of ester.

-To obtain high yield, used rxn with chloride

acids.Example:

O O
H2SO4
CH3CH2OH HOCCH3 CH3CH2OCCH3 H2O
ii. Formation of Inorganic Ester

-Involves rxn of alcohol with inorganic acids.

- The acids usually used are nitric acid, sulfuric acid and
phosphoric acid.
- The acids and products of esters are in the table below:

Table: Acids and inorganic esters produced from

alcohol.
Acids Ester
HONO , nitric acid RONO2, alkyl nitrate

HOSO3H, sulfuric acid ROSO3H, alkyl hydrogen sulfate

ROSO3R, dialkyl sulfate

H3PO4, phosphoric acid O

Alkyl dihydrogen
ROP(OH)2 phosphate

O O
sulfate ester CH3O-S-OH CH3O-S-OCH3
O O
methyl hydrogen sulfate dimethyl sulfate

phosphate ester O O
CH3O-P-OH CH3O-P-OH
OH OCH3
methyl dihydrogen phosphate dimethyl hydrogen phosphate
Synthesis of Nitroglycerine (glyceryl trinitrate)

-Glyceryl nitrate results from the reaction of glycerol (1,2,3-

propanetriol) with 3 molecules of nitric acid.
REACTIONS OF PHENOL

REACTIONS
OF PHENOL

ON THE AROMATIC RING ON THE -OH GROUP

a. Reduction a. Formation of Phenoxide salts

b. Esterification of Phenol

b. Electrophilic substitution
c. Ether Formation

d. Oxidation of Phenol to Quinone

REACTIONS OF PHENOL

A. Reactions on the Aromatic Ring

The phenolic ring can undergo these rxns below;
a. Reduction
OH OH
Ni
3H2
300oC

cyclohexanol

b. Electrophilic Substitution
-The OH group on the aromatic ring is an ortho/para
director for electrophilic substitution rxn on benzene
rings.
i. Br H2O
OH
OH
H2 O Br Br
3Br2
3HBr

Br
2,4,6-tribromophenol

ii. Dilute HNO3

OH OH OH

HNO3 , dilute
NO2
+

NO2
2-nitrophenol 4-nitrophenol
iii. Sulfonation in concn H2SO4
diethylether

OH SO3H OH
NO2
H2SO 4

o-
hydroxylbenzene SO 3H
sulfonic acid p-
hydroxylbenzene
sulfonic acid

B. Reactions on the OH group

a. Formation of Phenoxide Salts

-phenoxide salts are more acidic compared to alcohol.
-hence, phenol can react with aqueous NaOH to form
phenoxide salts.
-this rxn is used to differentiate between alcohol and
phenol. Examples:

Sodium phenoxide

ROH + NaOH No rxn

b. Esterification of Phenol
-rxn with chloride acids, will give ester.
-Rxn is in aqueous NaOH to give phenoxide salts.
-Phenol can also react with benzoic acid under reflux in
presence of an acidic catalyst to form phenyl benzoate.
Examples:
a.
O
OH ONa OCCH3
O
NaOH CH3CCl
NaCl
H 2O NaOH

b.
O O
H2SO 4 concn
OH COH OC

c. Formation of Ether
-rxn of phenol with alkyl halide in base.
Example:

K2CO3
OH CH3CH2Br OCCH3 HBr

d. Oxidation of Phenol to Quinone

-rxn of phenol with a strong oxidizing reagent to give
quinine (a conjugated 1,4-diketone)
-other strong oxidizing agents used are chromic acid and
Fremy salts (KSO3)2NO.
Examples:

CH3 CH3

Na2Cr2O 7
HO O O
H2SO4

(KSO3)2NO
HO O O
H2O

-O2 from air can also oxidize phenol to quinone through

free radical mechanism, a rxn called autooxidation.
Examples;

[O]
HO OH O O

Hydroquinone p-benzoquinone

OH O

[O]
OH O

Catechol o-benzoquinone